CN110655536A - Phosphorus-containing compound, phosphorus-containing flame retardant and preparation method and product thereof - Google Patents

Abstract

The present invention discloses a phosphorus-containing compound, a phosphorus-containing flame retardant and a preparation method thereof, as well as a resin composition comprising the above-mentioned phosphorus-containing flame retardant and a resin having an unsaturated bond. The resin composition can be made into various articles, such as prepreg, resin film, self-adhesive copper foil, laminate or printed circuit board, and has excellent properties in prepreg filling, flame retardancy, alkali resistance, glass transition temperature, At least one, more or all of the characteristics of thermal dimensional stability (ie, dimensional change rate after heating), heat resistance after moisture absorption, copper foil pulling force, dielectric constant and dielectric loss are unexpectedly improved.

Description

Phosphorus-containing compound, phosphorus-containing flame retardant and preparation method and product thereof

technical field

The present invention relates to a phosphorus-containing compound, a phosphorus-containing flame retardant, a preparation method thereof, a resin composition comprising the aforementioned resin composition, and articles made therefrom. In particular, it relates to a phosphorus-containing flame retardant and its resin composition which can be used to prepare prepregs, resin films, self-adhesive copper foils, laminates and printed circuit boards.

Background technique

As the information processing of electronic products such as mobile communications, servers, and cloud storage continues to develop towards the direction of high-frequency signal transmission and high-speed digitization, the selection of circuit board materials has become more stringent. In order to maintain the transmission rate and maintain the integrity of the transmission signal, the substrate material of the circuit board must have both low dielectric constant (Dk) and dielectric loss (also known as loss factor, dissipation factor, Df). At the same time, in order to maintain the normal operation of electronic components under high temperature and high humidity environment, the circuit board must also have the characteristics of heat resistance, humidity resistance and flame retardancy. On the other hand, in order to comply with the world's environmental protection trends and green regulations, halogen-free materials have become an environmental protection trend in the current electronics industry. Therefore, how to develop a halogen-free flame retardant high-performance printed circuit board (printed circuitboard, PCB) substrate is the direction of the current industry's active efforts.

In the prior art, in order to achieve the flame retardancy of UL94V-0 for environmentally friendly halogen-free laminates and printed circuit boards, phosphorus-containing flame retardants are usually added to their resin compositions, and phosphorus-containing flame retardants are preferably used. Derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), for example, 2-(10H-9-oxa-10-phospha-1-phenanthrene Base) Hydroquinone Phosphorus Oxide (DOPO-HQ for short), as an additive flame retardant, it has a high melting point and has little effect on the dimensional change rate of the substrate after being heated, but it has poor heat and humidity resistance and is prone to bursting at high temperatures. Another example is the phenolic resin containing DOPO, which can participate in the curing reaction, increase the glass transition temperature of the substrate and improve the resistance to heat and humidity. However, due to the presence of hydroxyl groups in the molecular structure, the dielectric constant and dielectric loss of the substrate are not good. (Dk and Df values are too high). DOPO modified polyphenylene ether resin has been used in the prior art to reduce the dielectric properties of the substrate and improve the heat resistance. However, the use of DOPO modified polyphenylene ether resin has low phosphorus content, poor flame retardant effect, and has Problems such as low copper foil tension and poor prepreg filling.

SUMMARY OF THE INVENTION

In view of the problems encountered in the prior art, in particular, the existing materials cannot satisfy the prepreg filling properties, the flame retardancy of the substrate, the low dielectric constant and low dielectric loss of the substrate, the high copper foil tension of the substrate, and the high glass transition of the substrate. One or more technical problems such as temperature, low dimensional change rate of the substrate, heat resistance of the substrate after moisture absorption, and alkali resistance of the substrate, etc., the present invention discloses a phosphorus-containing compound, which is represented by the following formula (1):

Wherein, m is an integer from 0 to 50, n is an integer from 2 to 25, and a is an integer from 0 to 23;

A and A' each independently represent the group after the dehydrogenation of the hydroxyl group of a dihydric phenol or a polyhydric phenol;

B represents the group after dechlorination of the dichloro compound;

D represents the group after the dehydrogenation of the hydroxyl group of the dihydric phenol or polyhydric phenol containing DOPO functional group;

Each of X independently represents a functional group containing a double bond or hydrogen, and each X is not hydrogen at the same time;

Y may be absent, or each independently represents a group represented by the following formula (2), or a hydrogen atom;

Wherein, q is an integer from 0 to 20, and A', B, D, and X are as defined in formula (1).

Preferably, the number average molecular mass (Mn) of the above A and A' is less than or equal to 1200.

In one embodiment, the A and A' include any one of the groups represented by the formula (3) to the formula (23) or any combination thereof, wherein p is an integer from 0 to 23, preferably It is any one of the structures represented by the following formula (3), formula (4), formula (5) and formula (6) or any combination thereof:

In one embodiment, the above-mentioned B includes any one of the groups represented by formula (24), formula (25) and formula (26) or any combination thereof:

In one embodiment, the above-mentioned D includes any one of the groups represented by formula (27) and formula (28) or any combination thereof:

In one embodiment, the above formula X is each independently any one of the groups represented by formula (29), formula (30), and formula (31):

R1 to R13 in formula (29), formula (30) and formula (31) are each independently one or more of a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group; Q is a covalent bond or has A functional group of at least one carbon atom, preferably, Q is a methylene group.

Preferably, the phosphorus-containing compound disclosed in the present invention includes any one of the structural formulas shown in the following formulas (32) to (38):

The present invention further discloses a phosphorus-containing flame retardant, comprising one or more of the above-mentioned phosphorus-containing compounds.

The present invention further discloses a resin composition comprising the above-mentioned phosphorus-containing flame retardant and a resin having an unsaturated bond.

Examples of the above-mentioned resin with unsaturated bonds are not particularly limited, and may include, but are not limited to, various resins with unsaturated bonds known in the art, and specific examples may include divinylbenzene (DVB), divinylbenzene Benzyl ether (bis(vinylbenzyl)ether, BVBE), 1,2-bis(vinylphenyl)ethane (1,2-bis(vinylphenyl)ethane, BVPE), triallyl isocyanurate ( triallyl isocyanurate, TAIC), triallyl isocyanurate prepolymer (pre-polymer TAIC), triallyl cyanurate (triallyl cyanurate, TAC), triallyl cyanurate prepolymer pre-polymer TAC, 1,2,4-trivinylcyclohexane (1,2,4-trivinylcyclohexane, TVCH), vinylbenzyl maleimide (VBM), diallyl Diallyl bisphenol A (DABPA), styrene, acrylates (such as methacrylate, tricyclodecane di(meth)acrylate or tri(meth)acrylate), vinyl polyphenylene ether Any one of resin, maleimide resin, polyolefin, or any combination thereof.

Unless otherwise specified, the aforementioned resins with unsaturated bonds may exist in the form of monomers, oligomers, polymers or any combination thereof or prepolymers thereof. For example, a resin with unsaturated bonds may comprise one or more monomers, oligomers, polymers, prepolymers, or any combination thereof.

In addition to the aforementioned phosphorus-containing flame retardants and resins with unsaturated bonds, the resin composition of the present invention may further comprise: epoxy resins, cyanate ester resins, phenol resins, benzoxazine resins, styrene resins as required Any one or any combination of maleic anhydride resin, polyester, amine curing agent, polyamide, polyimide.

In addition to the aforementioned phosphorus-containing flame retardants and resins with unsaturated bonds, the resin composition of the present invention may further comprise: flame retardants, inorganic fillers, hardening accelerators, solvents, silane coupling agents, surface active agents, if necessary. any one or any combination of agents, dyes, toughening agents.

For example, the resin composition of the present invention may include 5 parts by weight to 40 parts by weight of the above-mentioned phosphorus-containing flame retardant, and 50 parts by weight to 100 parts by weight of a resin having an unsaturated bond.

For example, the resin composition of the present invention may include 10 to 30 parts by weight of the above-mentioned phosphorus-containing flame retardant, and 50 to 100 parts by weight of a resin having an unsaturated bond.

The resin composition of the present invention can be made into various articles, including but not limited to prepreg, resin film, self-adhesive copper foil, laminate or printed circuit board.

The invention further discloses a preparation method of the above-mentioned phosphorus-containing flame retardant, which comprises the following steps: firstly reacting a dihydric phenol or a polyhydric phenol with a dichloro compound to obtain a first intermediate product; and then adding a dihydric phenol containing DOPO functional group or The metal salt of the polyhydric phenol continues to react to obtain the second intermediate product; and then vinyl halide is added for the reaction to obtain the phosphorus-containing flame retardant.

The invention discloses yet another preparation method of the above-mentioned phosphorus-containing flame retardant, which comprises: firstly reacting a first dihydric phenol or polyhydric phenol with a dichloro compound to obtain a first intermediate product; and then adding a second dihydric phenol The phenol or polyhydric phenol is reacted to obtain the second intermediate product; then the metal salt of dihydric phenol or polyhydric phenol containing DOPO functional group is added to continue the reaction to obtain the third intermediate product; then vinyl halide is added to react to obtain the Phosphorus flame retardant.

In the preparation method of the aforementioned phosphorus-containing flame retardant of the present invention, a phase transfer catalyst can be further added in the reaction process of the dihydric phenol or the polyhydric phenol and the dichloride compound.

Description of drawings

Figure 1 is the FTIR spectrum of product A1.

Detailed ways

In order for those skilled in the art to understand the features and effects of the present invention, general descriptions and definitions of terms and expressions mentioned in the specification and claims are hereinafter provided. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meanings understood by those skilled in the art to the present invention, and in case of conflict, the definitions in this specification shall prevail.

First of all, some parts of this document use "a", "an", "an" or similar terms to describe the components and technical features of the present invention. Such descriptions are only for convenience of expression and provide technical features of the present invention. general meaning. Accordingly, unless otherwise indicated, such descriptions should be read to include one or at least one and the singular also includes the plural.

As used herein, the terms "comprising," "including," "having," "containing," or any other similar term are open-ended transitional phrases intended to encompass non-exclusive inclusions. For example, a composition or article of manufacture containing a plurality of elements is not limited to only that element listed herein, but may also include other elements not expressly listed but generally inherent to the composition or article of manufacture. Otherwise, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" and not an exclusive "or". For example, the condition "A or B" is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), Both A and B are true (or exist). In addition, in this document, the terms "comprising", "including", "having", "containing" should be interpreted as having specifically disclosed and encompassing both "consisting of" and "substantially consisting of" and other closures Formal or semi-closed connectives.

In this document, all features or conditions defined as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered as encompassing and specifically disclosing all possible subranges and individual numerical values within the range, particularly integer numerical values. For example, a description of a range of "1 to 8" should be deemed to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly Sub-ranges are delimited by all integer values and should be deemed to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. Unless otherwise indicated, the foregoing method of interpretation applies to all content throughout this disclosure, whether broad or not.

If a quantity or other value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that any upper or preferred value of that range and any lower or preferred value of that range have been specifically disclosed herein. All ranges constituted by a value, whether or not such ranges are disclosed separately. Furthermore, when a range of values is referred to herein, unless otherwise indicated, the range shall include its endpoints and all integers and fractions within the range.

As used herein, numerical values should be understood to have the precision of the number of significant digits so long as the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

Where Markush group or option terminology is used herein to describe features or examples of the invention, those skilled in the art will recognize the Markush group or subgroup of all members within the option list or any individual member may also be used to describe the invention. For example, if X is described as "selected from the group consisting of X ₁ , X ₂ and X ₃ ", it also means that the claim that X is X ₁ and that X is X ₁ and/or X ₂ and/ Or X ₃ claims. Furthermore, with regard to the use of Markush group or option terminology to describe features or instances of the invention, those skilled in the art will appreciate any combination of subgroups or individual members of all members within a Markush group or option list. can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of X ₁ , X ₂ and X ₃ " and Y is described as "selected from the group consisting of Y ₁ , Y ₂ and Y ₃ " , then the claim that X is _X1 or _X2 or _X3 and Y is _Y1 or _Y2 or _Y3 has been fully described.

The following detailed description is merely exemplary in nature and is not intended to limit the invention and its uses. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or this summary or in the following detailed description or examples.

Phosphorus-containing compounds

One of the main objects of the present invention is to provide a phosphorus-containing compound, which is represented by the following formula (1):

Wherein, m is an integer from 0 to 50, n is an integer from 2 to 25, and a is an integer from 0 to 23;

A and A' each independently represent the group after the dehydrogenation of the hydroxyl group of a dihydric phenol or a polyhydric phenol;

B represents the group after dechlorination of the dichloro compound;

D represents the group after the dehydrogenation of the hydroxyl group of the dihydric phenol or polyhydric phenol containing DOPO functional group;

Each of X independently represents a functional group containing a double bond or hydrogen, and each X is not hydrogen at the same time;

Y may be absent, or each independently represents a group represented by the following formula (2), or a hydrogen atom;

Wherein, q is an integer from 0 to 20, and A', B, D, and X are as defined in formula (1).

Preferably, the number-average molecular mass (Mn) of the dehydrogenated groups of the above-mentioned A, A' dihydric phenols or polyhydric phenols is less than or equal to 1200.

In one embodiment, the A and A' include any one of the groups represented by the formula (3) to the formula (23) or any combination thereof, wherein p is an integer from 0 to 23, preferably It is any one of the structures represented by the following formula (3), formula (4), formula (5) and formula (6) or any combination thereof:

In one embodiment, the above-mentioned B includes any one of the groups represented by formula (24), formula (25) and formula (26) or any combination thereof:

In one embodiment, the above-mentioned D includes any one of the groups represented by formula (27) and formula (28) or any combination thereof:

In one embodiment, the above formula X is each independently any one of the groups represented by formula (29), formula (30), and formula (31):

R1 to R13 in formula (29), formula (30) and formula (31) are each independently one or more of a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group; Q is a covalent bond or has A functional group of at least one carbon atom, preferably, Q is a methylene group.

Preferably, the phosphorus-containing compound disclosed in the present invention includes any one of the structural formulas shown in the following formulas (32) to (38):

Phosphorus Flame Retardant

The present invention further provides a phosphorus-containing flame retardant, comprising one or more of the above-mentioned phosphorus-containing compounds.

Preparation method of phosphorus-containing flame retardant

First, the dihydric phenol or polyhydric phenol is reacted with the dichloro compound, and then the metal salt of the dihydric phenol or polyhydric phenol containing DOPO functional group is added for the reaction, and then the vinyl halide is added for the reaction, and the filtration is carried out to obtain the said compound containing the polyhydric phenol or polyhydric phenol. Phosphorus flame retardant.

Optionally, the aforementioned dihydric phenol or polyhydric phenol is preferably dihydric phenol, trihydric phenol or tetrahydric phenol, more preferably diallyl bisphenol A (DABPA), bisphenol A, trisphenol ethane, One or any combination of tetraphenolic ethane.

Optionally, the aforementioned dichloro compound is preferably one of bis(chloromethyl)benzene, bis(chloromethyl)biphenyl, and bis(chloromethyl)ether or any combination thereof.

The aforementioned metal salts of dihydric phenols or polyhydric phenols containing DOPO functional groups can be prepared by dissolving the alkali metal salts of dihydric phenols or polyhydric phenols containing DOPO functional groups and alcohols in a solvent, and then through the steps of refluxing, evaporating to dryness and drying. to make.

Optionally, the aforementioned alkali metal salts of alcohols are preferably potassium salts of alcohols, for example, the alkali metal salts of alcohols can be, but are not limited to, potassium ethoxide, potassium tert-butoxide or any combination thereof.

Optionally, the aforementioned solvent for dissolving the alkali metal salts of the DOPO functional group-containing dihydric or polyhydric phenol and alcohol may be, but not limited to, tetrahydrofuran (THF).

Optionally, the temperature of the reflux step during the preparation of the aforementioned DOPO functional group-containing dihydric phenol or polyhydric phenol metal salt is controlled within the range of 40 to 120° C. (for example, within the range of 60 to 120° C.), and the reaction time is 2 to 8 hours. .

Optionally, the aforementioned metal salt of the DOPO functional group-containing dihydric phenol or polyhydric phenol is preferably a potassium salt of the DOPO functional group-containing dihydric phenol or polyhydric phenol, for example, the metal salt of the DOPO functional group-containing dihydric phenol or polyhydric phenol can be Is but not limited to DOPO-HQ (2-(10H-9-oxa-10-phospha-1-phenanthryl)hydroquinone phosphorus oxide, or 10-(2,5-dihydroxyphenyl)-10H- 9-oxa-10-phosphaphenanthrene-10-oxide) potassium salt.

Alternatively, the aforementioned vinyl halide is preferably vinyl chloride. For example, the vinyl halide can be, but is not limited to, vinylbenzyl chloride, vinyl chloride, allyl chloride, acryloyl chloride, methacryloyl chloride, or any combination thereof.

Optionally, an appropriate amount of solvent, such as, but not limited to, ketone compounds (eg, acetone or methyl ethyl ketone), toluene, or any combination thereof, is added during the reaction of the dihydric or polyhydric phenol with the dichloride compound.

Optionally, a phase transfer catalyst, such as, but not limited to, tetrabutylammonium bromide, is further added during the reaction of the dihydric or polyhydric phenol with the dichloro compound.

Optionally, an alkaline solution such as, but not limited to, sodium hydroxide solution, potassium hydroxide solution, triethylamine or potassium tert-butoxide is further added during the reaction of the dihydric or polyhydric phenol with the dichloride compound.

In one embodiment of the present invention: firstly, the dihydric phenol or polyhydric phenol is reacted with the dichloro compound to obtain the first intermediate product; The metal salt of dihydric phenol or polyhydric phenol with phosphaphenanthrene-10-oxide) functional group continues to react to obtain a second intermediate product; then vinyl halide is added for reaction to obtain the phosphorus-containing flame retardant.

Optionally, the molar ratio of dihydric or polyhydric phenol to dichloro compound is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the molar ratio of the first intermediate product to the metal salt of the DOPO functional group-containing dihydric or polyhydric phenol is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the molar ratio of the second intermediate product to the vinyl compound is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the temperature of the reaction of the dihydric or polyhydric phenol and the dichloro compound is controlled to be in the range of 40 to 120°C (eg, in the range of 60 to 120°C), and the reaction time is 1 to 8 hours.

Optionally, the temperature of the reaction of the first intermediate product with the metal salt of the DOPO functional group-containing dihydric or polyhydric phenol is controlled to be in the range of 40 to 120° C. (eg, in the range of 60 to 120° C.), and the reaction time is 1 to 6 hours.

Optionally, the temperature of the reaction of the second intermediate product with the vinyl halide is controlled to be in the range of 40 to 120°C (eg, in the range of 60 to 120°C), and the reaction time is 1 to 6 hours.

Optionally, the reaction product of the second intermediate with vinyl halide is subjected to a water wash purification procedure.

More specifically, add diallyl bisphenol A, 1,4-p-dichlorobenzyl and toluene into the reaction tank, add alkaline sodium hydroxide solution, stir and mix evenly, and then add the phase transfer catalyst tetrabutyl bromide. ammonium chloride, and then the temperature was raised to 80 ° C and continued to stir for 4 hours to obtain the first intermediate product, and the potassium salt containing DOPO-HQ was continued to be added, and the temperature was maintained at 80 ° C and continued to stir for 2 hours to obtain the second intermediate product, and then added Vinylbenzyl chloride, maintaining the temperature at 80° C. and stirring continuously for 2 hours, and then performing the water washing and purification step, the flame retardant of the structure represented by formula (31) can be obtained.

In another embodiment of the present invention, the first dihydric phenol or polyhydric phenol is first reacted with a dichloro compound to obtain a first intermediate product; and then the second dihydric phenol or polyhydric phenol is added to react to obtain The second intermediate product; the metal salt of dihydric phenol or polyhydric phenol containing DOPO functional group is added to continue the reaction to obtain the third intermediate product; then vinyl halide is added for reaction to obtain the phosphorus-containing flame retardant.

Optionally, the molar ratio of the first dihydric or polyhydric phenol to the dichloro compound is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the molar ratio of the first intermediate product to the second dihydric or polyhydric phenol is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the molar ratio of the second intermediate product to the metal salt of the DOPO functional group-containing dihydric or polyhydric phenol is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the molar ratio of the third intermediate product to the vinyl compound is 8:1 to 1:25. For example but not limited to 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1: 5, 1:10, 1:15, 1:20, 1:25.

Optionally, the temperature of the reaction of the first dihydric or polyhydric phenol and the dichloro compound is controlled to be in the range of 40 to 120°C (eg, in the range of 60 to 120°C), and the reaction time is 1 to 8 hours.

Optionally, the temperature of the reaction of the first intermediate product with the second dihydric or polyhydric phenol is controlled to be in the range of 40 to 120°C (eg, in the range of 60 to 120°C), and the reaction time is 1 to 6 hours.

Optionally, the temperature of the reaction of the second intermediate product with the metal salt of the dihydric phenol or polyhydric phenol containing DOPO functional group is controlled to be in the range of 40 to 120° C. (for example, in the range of 60 to 120° C.), and the reaction time is 1 to 6 hours.

Optionally, the temperature of the reaction of the third intermediate product with the vinyl halide is controlled to be in the range of 40 to 120°C (eg, in the range of 60 to 120°C), and the reaction time is 1 to 6 hours.

Optionally, the reaction product of the third intermediate product and vinyl halide is subjected to a water washing purification procedure.

Other preparation steps not described in detail are the same as the aforementioned methods.

resin composition

The present invention also provides a resin composition comprising the above-mentioned phosphorus-containing flame retardant and a resin having an unsaturated bond.

Examples of the above-mentioned resins with unsaturated bonds are not particularly limited, and may include, but are not limited to, various resins with unsaturated bonds known in the art, such as but not limited to one of the following or any combination thereof: two Vinylbenzene (divinylbenzene, DVB), bis(vinylbenzyl)ether (BVBE), 1,2-bis(vinylphenyl)ethane (1,2-bis(vinylphenyl)ethane, BVPE) , triallylisocyanurate (triallylisocyanurate, TAIC), triallyl isocyanurate prepolymer (pre-polymer TAIC), triallyl cyanurate (triallyl cyanurate, TAC), Triallyl cyanurate prepolymer (pre-polymer TAC), 1,2,4-trivinyl cyclohexane (1,2,4-trivinyl cyclohexane, TVCH), vinylbenzylmaleimide Amine (vinyl benzylmaleimide, VBM), diallyl bisphenol A (DABPA), styrene, acrylate (eg: tricyclodecane di(meth)acrylate, tri(meth)acrylate) ), vinyl polyphenylene ether resin, maleimide resin, polyolefin.

Unless otherwise specified, the aforementioned resins with unsaturated bonds may exist in the form of monomers, oligomers, polymers or any combination thereof or prepolymers thereof. For example, a resin with unsaturated bonds may comprise one or more monomers, oligomers, polymers, prepolymers, or any combination thereof.

The vinyl polyphenylene ether resin used in the present invention is not particularly limited, and the vinyl polyphenylene ether resin can be any one or more polyphenylene ether resins suitable for the production of prepreg, resin film, laminate or printed circuit board, Specific examples include, but are not limited to: vinylbenzyl polyphenylene ether resin (eg OPE-2st, available from Mitsubishi Gas Chemical), methacrylic polyphenylene ether resin (eg SA-9000, available from Sabic), Vinylbenzyl modified bisphenol A polyphenylene ether or chain-extended polyphenylene ether. For example, the aforementioned chain-extended polyphenylene ethers may include the various polyphenylene ether resins disclosed in US Patent Application Publication No. 2016/0185904 Al, which is incorporated herein by reference in its entirety.

For example, the resin composition of each embodiment of the present invention may include 1 to 100 parts by weight of vinyl polyphenylene ether resin, such as 50 to 100 parts by weight of vinyl polyphenylene ether resin, and for example, 20 to 80 parts by weight of vinyl polyphenylene ether resin Vinyl polyphenylene ether resin, another example is 30 to 50 parts by weight of vinyl polyphenylene ether resin.

The maleimide resin used in the present invention is not particularly limited, and the maleimide resin is a compound, monomer, mixture, oligomer or polymer having more than one maleimide functional group in the molecule. Unless otherwise specified, the maleimide resin used in the present invention is not particularly limited, and can be any one or more suitable for prepregs, prepregs with copper foils, resin films, adhesive-backed copper foils, and laminates Or maleimide resin made of printed circuit boards. Specific examples include but are not limited to 4,4'-diphenylmethane bismaleimide (4,4'-diphenylmethane bismaleimide), oligomer of phenylmethane maleimide (or Polyphenylmethane maleimide (polyphenylmethane maleimide), m-phenylenebismaleimide (m-phenylenebismaleimide), bisphenol A diphenyl etherbismaleimide (bisphenol A diphenyl etherbismaleimide) , 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4 ,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6-bismaleimide- (2,2,4-trimethyl)hexane (1,6-bismaleimide-(2,2,4-trimethyl hexane)), 2,3-dimethylbenzenemaleimide (N-2, 3-xylylmaleimide), 2,6-dimethylbenzenemaleimide (N-2,6-xylenemaleimide), N-phenylmaleimide (N-phenylmaleimide), the At least one or any combination of the prepolymer of the imide compound and the above-mentioned compound. Wherein, the prepolymer can be, for example, the prepolymer of diallyl compound and maleimide compound, the prepolymer of diamine and maleimide compound, polyfunctional amine and maleimide Prepolymers of phenolic compounds or prepolymers of acidic phenolic compounds and maleimide compounds, etc.

For example, the maleimide resin can be traded under the trade names BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, Maleimide resins such as BMI-5000, BMI-5100, BMI-TMH, BMI-7000 and BMI-7000H produced by Daiwakasei Company, or BMI-70, BMI-80, etc. produced by KI Chemical Company. imide resin.

For example, the maleimide resin containing aliphatic long chain structure can be traded under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI- 6000 and other maleimide resins produced by Designer Molecular Company.

For example, the resin composition of each embodiment of the present invention may include 1 to 100 parts by weight of maleimide resin, such as 50 to 100 parts by weight of maleimide resin, and for example, 5 to 50 parts by weight of maleimide resin Maleimide resin.

For example, the olefin polymer used in the present invention is not particularly limited, and may be any one or more of commercially available products or any combination thereof. Specific examples include, but are not limited to, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urethane oligomer (vinyl-polybutadiene-urethane oligomer), styrene butadiene copolymer, hydrogenated styrene butadiene copolymer, styrene isoprene copolymer, hydrogenated styrene isoprene copolymer, polybutylene At least one or any combination of diene, methylstyrene copolymer, petroleum resin and cyclic olefin copolymer.

For example, the resin composition of various embodiments of the present invention may include 1 to 100 parts by weight of the olefin polymer, eg, 5 to 50 parts by weight of the olefin polymer.

Unless otherwise specified, the amount of any one of the aforementioned phosphorus-containing flame retardants and resins with unsaturated bonds, and the proportional relationship between them, can be adjusted as needed.

In one embodiment, the resin composition of the present invention includes 5 to 40 parts by weight of the above-mentioned phosphorus-containing flame retardant, and 50 to 100 parts by weight of a resin having an unsaturated bond.

In a preferred embodiment, the resin composition of the present invention comprises 10 to 30 parts by weight of the above-mentioned phosphorus-containing flame retardant, and 50 to 100 parts by weight of a resin having an unsaturated bond.

In addition to the aforementioned two components, the resin composition of the present invention may optionally further comprise epoxy resin, cyanate ester resin, phenol resin, benzoxazine resin, styrene maleic anhydride resin, polyester, amine type curing agent, polyamide, polyimide, or any combination thereof.

Unless otherwise specified, the amount of any of the foregoing components may be between 1 and 100 parts by weight compared to the total of 1 to 100 parts by weight of the phosphorus-containing flame retardant and the resin having an unsaturated bond.

For example, the above epoxy resins can be various types of epoxy resins known in the art, including but not limited to, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin Epoxy resin, novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) ring Oxygen resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin (such as naphthol epoxy resin), benzofuran epoxy resin, Isocyanate-modified epoxy resins. The novolac epoxy resin can be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin Epoxy resin, phenol benzaldehyde epoxy resin, phenolaralkyl novolac epoxy resin or o-cresol novolac epoxy resin; among them, phosphorus-containing epoxy resin The resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or any combination thereof. The aforementioned DOPO epoxy resin can be selected from DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin and DOPO-containing bisphenol A epoxy resin One, two or more of DOPO-containing bisphenol-A novolac epoxy resins; the aforementioned DOPO-HQ epoxy resins can be selected from DOPO-HQ phenol novolac epoxy resins (DOPO-HQ -containing phenolic novolacepoxy resin), DOPO-HQ-containing cresol novolacepoxy resin and DOPO-HQ-containing bisphenol-Anovolac one, two or more of epoxy resins.

For example, the cyanate ester resin is not particularly limited, any cyanate ester with Ar-O-C≡N structure can be used, wherein Ar can be substituted or unsubstituted aromatic, phenolic, bisphenol A, bisphenol A novolac, bisphenol F, bisphenol F novolac or phenolphthalein. The above-mentioned cyanate resins may be, for example, under the trade names primaset PT-15, PT-30S, PT-60S, CT-90, BADCY, BA-100-10T, BA-200, BA-230S, BA-300S, BTP- 2500, BTP-6020S, DT-4000, DT-7000, Methylcy or ME-240S and other cyanate resins produced by Lonza.

For example, phenolic resins include, but are not limited to, monofunctional, difunctional, or polyfunctional phenolic resins, including phenolic resins known to be used in resin compositions for making prepregs, such as phenolic resins, phenolic resins, and the like.

For example, benzoxazine resins include, but are not limited to, bisphenol A-type benzoxazine resins, bisphenol F-type benzoxazine resins, phenolphthalein-type benzoxazine resins, dicyclopentadiene benzoxazine resins , Phosphorus-containing benzoxazine resin, diaminodiphenyl ether type benzoxazine resin or unsaturated bond-containing benzoxazine resin, such as but not limited to the trade names LZ-8270, LZ-8280 or LZ- 8290, or the trade name HFB-2006M produced by Showa Polymer Corporation.

For example, in the aforementioned styrene maleic anhydride resin, the ratio of styrene (S) to maleic anhydride (MA) can be 1/1, 2/1, 3/1, 4/1, 6/1, 8 /1 or 12/1, such as styrene maleic anhydride copolymers sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80.

For example, the polyester can be various types of polyester resins known in the art, including but not limited to various commercially available polyester resin products. For example, but not limited to, the trade name HPC-8000T65 sold by Dainippon Ink Chemicals.

For example, the aforementioned amine curing agent may include, but is not limited to, at least one of diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide, or any of them. a combination.

For example, the aforementioned polyamides can be various types of polyamide resins known in the art, including but not limited to various commercially available polyamide resin products.

For example, the aforementioned polyimide can be various types of polyimide resins known in the art, including but not limited to various commercially available polyimide resin products.

On the other hand, in addition to the aforementioned components, the resin composition of the present invention may optionally further comprise a flame retardant, an inorganic filler, a hardening accelerator, a solvent, a silane coupling agent, a surfactant, a coloring agent, an enhancer toughener, or any combination thereof. Unless otherwise specified, the amount of any of the foregoing components may be between 1 and 100 parts by weight compared to the total of 1 to 100 parts by weight of the phosphorus-containing flame retardant and the resin having an unsaturated bond.

For example, compared to 100 parts by weight of the above-mentioned phosphorus-containing flame retardant and resin having an unsaturated bond, the flame retardant used in the present invention is not particularly limited, and the amount thereof may be 1 part by weight to 100 parts by weight.

The flame retardant used in the present invention can be any one or more flame retardants suitable for making prepregs, resin films, adhesive-backed copper foils, laminates or printed circuit boards, such as but not limited to phosphorus-containing flame retardants, Preferably, it can be selected from at least one, two or any combination of two or more of the following groups: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate) (hydroquinone bis- (diphenyl phosphate)), bisphenol A bis-(diphenylphosphate) (bisphenol A bis-(diphenylphosphate)), tri(2-carboxyethyl)phosphine (TCEP), phosphoric acid Tris(chloroisopropyl) ester, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis-(xylyl phosphate) (resorcinol bis) (dixylenyl phosphate), RDXP, such as PX-200, PX-201, PX-202 and other commercial products), phosphazene (such as SPB-100, SPH-100, SPV-100 and other commercial products), many Melamine polyphosphate, DOPO and its derivatives (such as double DOPO compounds) or resins, DPPO (diphenylphosphine oxide) and its derivatives (such as double DPPO compounds) or resins, melamine cyanurate (melamine cyanurate) and Hydroxyethyl isocyanurate (tri-hydroxy ethyl isocyanurate) or aluminum phosphate (such as OP-930, OP-935 and other products).

For example, the flame retardant can be a DPPO compound (eg, bis-DPPO compound), DOPO compound (eg, bis-DOPO compound), DOPO resin (eg, DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO bond Bonded epoxy resin, etc., where DOPO-PN is DOPO phenol novolac compound, DOPO-BPN can be DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac) or DOPO-BPSN (DOPO- bisphenol S novolac) and other bisphenol novolac compounds.

Unless otherwise specified, compared to 100 parts by weight of the above phosphorus-containing flame retardant and resin with unsaturated bonds, the inorganic filler used in the present invention is not particularly limited, and the amount thereof can be 10 parts by weight to 300 parts by weight.

The inorganic filler can be any one or more inorganic fillers suitable for prepreg, resin film, self-adhesive copper foil, laminate or printed circuit board production, specific examples include but are not limited to: silica (fused, non-fused aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica , boehmite (boehmite, AlOOH), calcined talc, talc, silicon nitride or calcined kaolin. In addition, the inorganic filler can be spherical, fibrous, plate, granular, flake or needle-like, and can be selectively pretreated with a silane coupling agent.

For example, the hardening accelerator (including the hardening initiator) may include a catalyst such as Lewis base or Lewis acid. Wherein, the Lewis base can include imidazole (imidazole), boron trifluoride amine complex, ethyltriphenyl phosphonium chloride (ethyltriphenyl phosphonium chloride), 2-methylimidazole (2-methylimidazole, 2MI), 2-phenyl Imidazole (2-phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4MI), triphenylphosphine (TPP) and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). The Lewis acid may contain metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc and other metal salt compounds, such as metal catalysts such as zinc octoate and cobalt octoate. Preferably, the hardening accelerator (including the hardening initiator) comprises a free radical generating peroxide, including but not limited to: dicumyl peroxide, t-butyl peroxybenzoate, dibenzoyl peroxide (dibenzoyl peroxide, BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B) and bis(tert-butylperoxyisopropyl)benzene or any combination thereof.

The main function of adding a solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition. For example, solvents may include, but are not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, diethyl ether Toluene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, etc. solvent or its mixed solvent.

The silane coupling agent can include silane compounds (such as but not limited to siloxane), which can be divided into amino silane compounds and epoxy silane compounds according to the types of functional groups. , vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanato silane compounds, methacryloxy silane compounds and acryloxy silane compounds.

The main function of adding surfactants is to make the inorganic fillers uniformly dispersed in the resin composition.

For example, the aforementioned colorants may include, but are not limited to, dyes or pigments.

The main function of adding a toughening agent is to improve the toughness of the resin composition. The toughening agent may include, but is not limited to, rubber resin, carboxyl-terminated butadiene acrylonitrilerubber (CTBN), core-shell rubber and other compounds or any combination thereof.

Articles made of resin compositions

The resin compositions of various embodiments of the present invention can be processed into various types of articles, including but not limited to prepregs, resin films, self-adhesive copper foils, laminates or printed circuit boards.

For example, the resin composition of each embodiment of the present invention can be made into a prepreg.

For example, each resin composition can be uniformly mixed to form a varnish, the varnish can be placed in an impregnation tank, and then the glass fiber cloth can be dipped into the impregnation tank to make the resin composition adhere to the glass fiber cloth, and then heated appropriately. The temperature is heated and baked to a semi-cured state, and a pre-preg sheet can be obtained.

In one embodiment, the prepreg of the present invention has a reinforcing material and a layered object disposed on the reinforcing material, and the layered object is heated to a semi-cured state (B-stage ) is made. The baking temperature for making the prepreg is, for example, between 120°C and 180°C. The reinforcing material may be any one of fiber material, woven cloth, non-woven fabric, liquid crystal resin film, PET film (polyester film) and PI film (polyimide film), and the woven cloth preferably contains glass fiber cloth. The type of glass fiber cloth is not particularly limited, and it can be commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth , L-type glass fiber cloth or NE-type glass fiber cloth, the types of fibers include yarn and roving, etc., and the form can include open fiber or no open fiber. The aforementioned nonwoven fabric preferably includes a liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, and the like, and is not limited thereto. The aforementioned woven fabric may also include a liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., and is not limited thereto. The reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be optionally pretreated with a silane coupling agent. After the prepreg is subsequently heated and cured (C-stage), an insulating layer will be formed.

The article made from the aforementioned resin composition can also be a resin film, and the resin film is formed by baking and heating the resin composition to a semi-cured state, wherein the resin composition can be selectively coated on polyethylene terephthalic acid On the polyethylene terephthalate film (PET film) or the polyimide film (polyimide film), the resin film is formed by heating and baking at an appropriate heating temperature to a semi-cured state.

The article made from the aforementioned resin composition can be a self-adhesive copper foil, and a manufacturing method of the resin-coated copper foil (RCC) can be to apply the resin composition of each embodiment of the present invention to the copper foil respectively On the surface, the resin composition is uniformly adhered, and then heated and baked at an appropriate temperature to a semi-cured state to obtain a self-adhesive copper foil.

In one embodiment, the resin composition of the present invention can be made into various laminates such as copper foil substrates, which include two copper foils and an insulating layer, and the insulating layer is arranged between the two copper foils , and the insulating layer can be cured by the aforementioned resin composition at high temperature and high pressure (C-stage), and the applicable curing temperature is between 190°C and 220°C, preferably between 200°C and 210°C. , the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. The above-mentioned insulating layer may be obtained by curing the above-mentioned prepreg or resin film. The material of the metal foil can be copper, aluminum, nickel, platinum, silver, gold or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

In one embodiment, the aforementioned laminate can be further processed through a circuit manufacturing process to form a printed circuit board.

One of the ways of making the printed circuit board of the present invention can be to use a double-sided copper clad laminate with a thickness of 28 mils (mil) and with 1 ounce (ounce) of HTE (High Temperature Elongation) copper foil (for example, product EM-827, Can be purchased from Taiwan Optoelectronics Materials), drilled and then electroplated to form electrical conduction between the upper copper foil and the bottom copper foil. The upper layer copper foil and the bottom layer copper foil are then etched to form an inner layer circuit. Then, the inner layer circuit is subjected to browning and roughening treatment to form a concave-convex structure on the surface to increase the roughness. Next, stack the copper foil, the prepreg, the inner layer circuit, the prepreg, and the copper foil in sequence, and then use a vacuum lamination device to heat for 90 to 180 minutes at a temperature of 190 to 220° C. to cure the insulating layer material of the prepreg . Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the ultra-thin copper foil on the outermost surface to obtain a printed circuit board.

For example, the resin composition disclosed in the present invention and various articles prepared therefrom preferably have any one or any combination of the following properties:

The glass transition temperature measured by the dynamic mechanical analyzer (DMA) with reference to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 210°C, for example, the glass transition temperature is between 210°C and 230°C, and for example, the glass transition temperature between 210°C and 220°C.

Z-axis dimensional change is less than or equal to 2.5% as measured by a thermomechanical analyzer (TMA) with reference to the method described in IPC-TM-650 2.4.24.5, eg, Z-axis dimensional change from between 2.2% and 2.5% between.

With reference to IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, the moisture absorption and heat resistance measured by the method described in .

The flame retardancy measured with reference to the UL94 standard method reaches the V-0 level.

Refer to IPC-TM-650 2.4.8 to measure the copper foil pull force greater than or equal to 4.0lb/inch, for example, the copper foil pull force is between 4.1lb/inch to 4.6lb/inch.

The dielectric constant measured at a frequency of 10 GHz with reference to JIS C2565 is less than or equal to 3.9, such as a dielectric constant between 3.7 and 3.9, such as a dielectric constant between 3.7 and 3.8; and

The dielectric loss measured at a frequency of 10 GHz with reference to the method described in JIS C2565 is less than or equal to 0.0055, for example, the dielectric loss is between 0.0048 and 0.0053.

In one embodiment, the prepreg fillability of the prepreg measured by the prepreg fill is greater than or equal to 80%.

In one embodiment, the alkali resistance time of the aforementioned laminated board measured by alkali resistance is greater than or equal to 15 minutes, for example, between 15 minutes and 20 minutes.

specific embodiment

The examples of the present invention use various raw materials from the following sources, respectively prepare the resin compositions of the examples of the present invention and the comparative examples of the present invention according to the dosages in Tables 1 to 2, and Tables 5 to 6, and further prepare various types of tests. sample or item.

The chemical reagents used in the following examples and comparative examples are as follows:

1. Diallyl bisphenol A (DABPA), trade name: DABPA, purchased from Laizhou Laiyu Chemical Co., Ltd.

2. Bisphenol A, trade name: B802575, purchased from Shanghai McLean Biochemical Technology Co., Ltd.

3. Trisphenol ethane, trade name: HWG18665, purchased from Beijing Huawei Ruike Chemical Co., Ltd.

4. Tetraphenolic ethane, trade name: TPN1, purchased from Nanya Plastics.

5. 2-(10H-9-oxa-10-phospha-1-phenanthryl)hydroquinone phosphorus oxide (DOPO-HQ), trade name: CG-DOPO-HQ, purchased from Nanjing Hengqiao Chemical Technology Materials Co., Ltd. company.

6. Vinylbenzyl chloride (VBC), trade name: C1792, purchased from Tixiai (Shanghai) Chemical Industry Development Co., Ltd.

7. 1,4-p-dichlorobenzyl, or Α,Α'-dichloro-1,4-xylene, trade name: D104515, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

8. Triallyl isocyanurate, trade name: TAIC, purchased from Qinyu Enterprise Co., Ltd.

9. Bismaleimide, trade name: KI-70, purchased from KI Chemistry.

10. Divinylbenzyl polyphenylene ether resin, trade name: OPE-2st, purchased from Mitsubishi Gas Chemical Company.

11. A vinyl-terminated phosphorus-containing polyphenylene ether resin, P-PPO, synthesized with reference to the formula (V) described in US Patent Publication No. 2017/0088669A1 and its production method.

12. DOPO derivatives, bis-DOPO compounds, are synthesized with reference to the formula (Ia) described in US Patent Publication No. 2017/0166729A1 and its production method.

13. Phosphorus-containing phenolic resin, trade name: XZ92741, purchased from Lanke Chemical (Zhangjiagang) Co., Ltd.

14. Styrene-butadiene-divinylbenzene copolymer, trade name: Ricon 257, available from Cray Valley Company.

15. Butadiene-styrene copolymer, trade name: Ricon 184, available from Cray Valley Company.

16. Spherical silica, trade name: SFP-30MK, purchased from DENKA Denka Corporation.

17. 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne (2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne), Trade name: 25B, purchased from Nippon Oil Co., Ltd.

Components A1 to A5 used in Examples E1 to E13 correspond to the products obtained in Preparation Examples 1 to 5, respectively. The components A6 to A8 used in Comparative Examples C1 to C13 correspond to the products obtained in Preparation Examples 6 to 8, respectively.

Preparation Example 1

Add 0.2 mol (35 g) of 1,4-p-dichlorobenzyl, 0.1 mol (30.8 g) of diallyl bisphenol A (DABPA) and 120 g of toluene solvent into the stirring tank, and then add 40.0 g of 20% NaOH aqueous solution , then added 16.1 g of tetrabutylammonium bromide, then the temperature was raised to 80 ° C and continued to stir for 4 hours to obtain the first intermediate product; continue to add 0.2 mol (79.2 g) potassium salt of DOPO-HQ (0.1 mol (79.2 g) DOPO-HQ and 0.1 mol (22.4 g) potassium tert-butoxide were dissolved in tetrahydrofuran (THF) solvent, the temperature was controlled at 80°C, refluxed for 6 hours, and then evaporated to dryness and dried to obtain DOPO-HQ potassium salt) , maintain 80 ℃ and continue to stir and react for 2 hours to obtain the second intermediate product; then add 0.2 moles (30.6 grams) of vinylbenzyl chloride (VBC), maintain 80 ℃ and continue to stir and react for 2 hours, and then carry out washing and purification procedure , the product A1 is obtained.

The product A1 (Product A1) obtained in Preparation Example 1 was analyzed by Fourier transform infrared spectroscopy (FTIR). The comparison results are shown in Figure 1. The results show that the product of Preparation Example 1 is at 1462.37cm ^-1 and 1295.40cm P-Ar vibration peak and P=O absorption peak in DOPO-HQ appeared at ^-1 , CH stretching vibration peak on CH ₃ in DABPA appeared at 2967.50cm ^-1 , and ethylene appeared at 995.29cm ^-1 and 911.56cm ^-1 The characteristic peak of the double bond in the benzyl chloride (VBC), and the characteristic peak of the phenolic hydroxyl group of the reactant diallyl bisphenol A ( ^DABPA ) at 3435.29 cm disappears, so the result can confirm that the obtained product is the product of the present invention. Phosphorus-containing flame retardants.

Preparation Example 2

Add 0.3 mol (52.5 g) of 1,4-p-dichlorobenzyl, 0.1 mol (30.6 g) of trisphenol ethane and 120 g of toluene solvent into the stirring tank, then add 60.0 g of 20% NaOH aqueous solution, and then add 16.1 g Tetrabutylammonium bromide, then the temperature was raised to 80°C and stirring was continued for 4 hours to obtain the first intermediate product; 0.3 moles (118.8 g) of potassium salt of DOPO-HQ were continuously added, maintained at 80°C and continued to stir for 2 hour, the second intermediate product was obtained; then 0.3 moles (45.9 g) of vinylbenzyl chloride (VBC) were added, maintained at 80° C. and continued to stir and react for 2 hours, and then washed and purified to obtain product A2.

Preparation Example 3

Add 0.4 moles (70.0 grams) of 1,4-p-dichlorobenzyl, 0.1 moles (38.2 grams) of tetraphenolic ethane and 120 grams of toluene solvent into the stirring tank, then add 80.0 grams of 20% NaOH aqueous solution, and then add 16.1 grams Tetrabutylammonium bromide, then the temperature was raised to 80°C and stirring was continued for 4 hours to obtain the first intermediate product; 0.4 moles (164.0 g) of potassium salt of DOPO-HQ were continued to be added, maintained at 80°C and the reaction was continued to stir for 2 hour, the second intermediate product was obtained; 0.4 moles (61.2 g) of vinylbenzyl chloride (VBC) were added, maintained at 80° C. and the reaction was continued to stir for 2 hours, followed by washing and purification procedure to obtain product A3.

Preparation Example 4

Add 0.8 mol (140.0 g) 1,4-p-dichlorobenzyl, 0.1 mol (38.2 g) tetraphenolic ethane and 240 g toluene solvent into the stirring tank, then add 160.0 g of 20% NaOH aqueous solution, and then add 16.1 g Tetrabutylammonium bromide, then the temperature was raised to 80°C and stirring was continued for 4 hours to obtain the first intermediate product, and 0.4 moles (123.2 g) of diallyl bisphenol A (DABPA) were added, and the temperature was maintained at 80°C and Continue to stir and react for 2 hours to obtain the second intermediate product; continue to add 0.4 mol (164.0 g) potassium salt of DOPO-HQ, maintain 80° C. and continue to stir and react for 2 hours to obtain the third intermediate product; then add 0.4 mol ( 61.2 g) vinylbenzyl chloride (VBC), maintained at 80° C. and continued to stir the reaction for 2 hours, and then carried out a water washing purification procedure to obtain the product A4.

Preparation Example 5

Add 0.2 mol (35 g) 1,4-p-dichlorobenzyl, 0.1 mol (22.8 g) bisphenol A (BPA) and 120 g toluene solvent into the stirring tank, then add 40.0 g of 20% NaOH aqueous solution, and then add 16.1 g g tetrabutylammonium bromide, then the temperature was raised to 80 ° C and continued to stir for 4 hours to obtain the first intermediate product; continue to add 0.2 moles (79.2 g) of potassium salt of DOPO-HQ, maintain 80 ° C and continue to stir the reaction After 2 hours, the second intermediate product was obtained; then 0.2 moles (30.6 g) of vinylbenzyl chloride (VBC) were added, maintained at 80° C. and the stirring reaction was continued for 2 hours, followed by washing and purification procedure to obtain product A5.

Preparation Example 6

Add 0.1 mol (17.5 g) 1,4-p-dichlorobenzyl and 0.2 mol (79.2 g) potassium salt of DOPO-HQ and 120 g toluene solvent into the stirring tank, then add 40.0 g of 20% NaOH aqueous solution, and then add 16.1 g Gram tetrabutylammonium bromide, then the temperature was raised to 80 ° C and continued to stir for 4 hours, then 0.2 moles (30.6 g) of vinylbenzyl chloride (VBC) were added, maintained at 80 ° C and continued to stir for 2 hours, then A water wash purification procedure was carried out to give product A6.

Preparation Example 7

Add 0.1 mole (17.5 g) of 1,4-p-dichlorobenzyl, 0.2 mole (61.6 g) of diallyl bisphenol A (DABPA) and 120 g of toluene solvent into the stirring tank, and then add 40.0 g of 20% NaOH aqueous solution , then added 16.1 grams of tetrabutylammonium bromide, then the temperature was raised to 80 ° C and continued to stir for 4 hours, then 0.2 moles (30.6 grams) of vinylbenzyl chloride (VBC) were added, and 60.0 grams of 20% NaOH aqueous solution was added. , maintained at 80 °C and continued to stir the reaction for 2 hours, and then carried out the water washing purification procedure to obtain the product A7.

Preparation Example 8

Add 0.3 mol (52.5 g) of 1,4-p-dichlorobenzyl, 0.1 mol (30.6 g) of trisphenol ethane and 120 g of toluene solvent into the stirring tank, then add 60.0 g of 20% NaOH aqueous solution, and then add 16.1 g Tetrabutylammonium bromide, then the temperature was raised to 80 ° C and continued to stir for 4 hours, then 0.3 moles (45.9 g) of vinylbenzyl chloride (VBC) were added, and 60.0 g of 20% NaOH aqueous solution was added, maintained at 80 ° C and Continue to stir the reaction for 2 hours, and then carry out the water washing purification procedure to obtain the product A8.

The characteristic tests of Examples E1-E13 and Comparative Examples C1-C13 were made by referring to the following methods to make the objects to be tested (samples), and then carried out according to specific test conditions. The results are listed in Table 3, Table 4, Table 7, and Table 8.

1. Prepreg: respectively select the resin composition of the above-mentioned embodiment (listed in Table 1 to Table 2) and the resin composition of the above-mentioned comparative example (listed in Table 5 to Table 6), after the respective resin compositions are uniformly mixed A varnish is formed, the varnish is placed in an impregnation tank, and a glass fiber cloth (for example, E-glass fiber fabric using 2116, available from Asahi) is dipped into the impregnation tank, so that The resin composition was attached to the glass fiber cloth, and was heated and baked at 145° C. for about 4 minutes to obtain a prepreg.

2. Substrate containing copper foil (5-ply, five sheets of prepreg laminated): prepare two RTF (reverse treated copper foil) copper foils with a thickness of 18 microns and five sheets of 2116 glass fiber cloth to impregnate the samples to be tested ( The prepregs prepared in each group of Examples or Comparative Examples), each with a resin content of about 55%, were stacked in the order of one RTF copper foil, five prepregs and one RTF copper foil, under vacuum conditions. , The pressure is 30kgf/cm ² , and the copper-containing foil substrate is formed by pressing at 200° C. for 2 hours. Among them, five prepregs stacked on each other are cured to form an insulating layer between two copper foils, and the resin content of the insulating layer is about 55%.

3. Copper-free substrate (5-ply, formed by laminating five prepregs): The above-mentioned copper-containing substrate is etched to remove two copper foils to obtain a copper-free substrate (5-ply), which does not contain copper. The substrate is made of five prepreg sheets, and the resin content of the copper-free substrate is about 55%.

4. Copper-free substrate (2-ply, formed by laminating two prepregs): prepare two RTF (reversetreated copper foil) copper foils with a thickness of 18 microns and two 2116 glass fiber cloths to impregnate the samples to be tested (each A set of prepregs prepared in Examples or Comparative Examples), each with a resin content of about 55%, were stacked in the order of one RTF copper foil, two prepregs and one RTF copper foil, under vacuum conditions, The copper foil-containing substrate was formed by pressing at a pressure of 30 kgf/cm ² and 200° C. for 2 hours. Among them, two prepregs stacked on each other are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 55%. The above copper-containing substrate is etched to remove two copper foils to obtain a copper-free substrate (2-ply). 55%.

For the aforementioned analytes, characteristic analysis was carried out in the following manner.

1. Glue-filling properties of prepreg:

Take 11 prepregs made of 2116 E-glass fiber cloth impregnated with each sample to be tested (each group of examples or comparative examples), and superimpose a 1-ounce HTE (high temperature elongation) copper foil on the top and bottom respectively , and then press to form a copper foil substrate, and drill holes on the surface of the copper foil substrate to form a core substrate with through holes. Laminate a prepreg made of 2116 E-glass cloth and 1 oz of HTE copper foil in sequence under it, laminate a release film on top of it, and press again to form a second copper foil substrate. Remove the release film on the surface of the copper foil substrate, observe whether the through hole is filled, and record the through hole filling rate.

2. Flame retardancy

In the flame retardant test, the above-mentioned copper-free substrate (made by pressing five prepreg sheets) (125mm×13mm) was selected as the sample to be tested; the measurement was carried out according to the UL94 standard method, and the flame retardant analysis results were V-0, V -1, V-2 grade indicates that V-0 flame retardancy is better than V-1 flame retardancy, V-1 flame retardancy is better than V-2 flame retardancy, and the sample burns out is the worst.

3. Alkali resistance

Select the above-mentioned copper-free substrate (five pieces of prepreg laminated) as the sample to be tested, cut out 3 test strips of 4mm × 2mm, put it into a 105 ℃ oven for 2 hours, and then soak it in 20% of 90 ℃ In the NaOH solution, take it out every 5 minutes, visually observe whether the appearance of the substrate appears whitish or the texture is revealed, and record the soaking time of the sample. If whitening or texture is revealed, it means that the base material does not pass the alkali resistance within this time range, and the sample needs to be re-made and taken out every 1 minute, and visually observe when the base material will appear whitish or textured. The pattern is revealed, and the soaking time of the sample is recorded. The longer the time, the better the alkali resistance.

4. Glass transition temperature (glass transition temperature, Tg)

In the measurement of the glass transition temperature, a copper-free substrate (formed by laminating five prepreg sheets) was selected as the sample to be tested. A dynamic mechanical analyzer (DMA) was used to measure the glass transition of each sample to be tested by referring to the method described in IPC-TM-6502.4.24.4 Glass Transition and Modulus of Materials Used in High Density Interconnection (HDI) and Microvias-DMA Method Temperature, in °C. The measurement temperature range is 35-270°C, the temperature rise rate is 2 (°C/min), and the higher the glass transition temperature, the better.

5. Rate of dimensional change (z-axis)

In the measurement of the dimensional change rate, a copper-free substrate (formed by pressing five prepreg sheets) was selected as the sample to be tested for thermal mechanical analysis (TMA). The sample is heated at a temperature rise rate of 10°C per minute, and the temperature is increased from 50°C to 260°C. Refer to the method described in IPC-TM-650 2.4.24.5 to measure the Z-axis dimensional change rate of each sample to be tested (unit: %) , the lower the percentage of dimensional change, the better, and the difference in dimensional change rate is greater than or equal to 0.1%, which is a significant difference.

6. Hygroscopic heat resistance test (pressure cooking test):

The copper-free substrate obtained by etching the copper foil on the surface of the copper foil substrate (formed by pressing five prepregs) was subjected to pressure cooking test (PCT) with reference to the method described in IPC-TM-650 2.6.16.1. After 5 hours of moisture absorption test, refer to the method described in IPC-TM-650 2.4.23, use the above-mentioned moisture absorption-free copper-free substrate, and immerse each sample to be tested in a tin furnace with a constant temperature of 288 °C for 20 seconds. , after taking it out, observe whether the explosion board occurs. If the test result is explosion board (marked X), it means that the insulating layer of the substrate is partially separated between layers. If the test result is an unexploded board (marked O), it means that no interlayer peeling has occurred. A total of three samples to be tested are analyzed in this test.

7. Copper foil tensile strength (peeling strength, P/S)

Select the above-mentioned copper-containing substrate (formed by pressing five prepreg sheets) as the sample to be tested, and use a universal tensile strength tester to measure the copper foil tensile force according to the method described in IPC-TM-650 2.4.8.

8. Dielectric constant (Dk) and dielectric loss (dissipation factor, Df):

In the measurement of dielectric constant and dielectric loss, the above-mentioned copper-free substrate (made by pressing two prepregs) was selected as the sample to be tested, and a microwave dielectric analyzer (microwave dielectrometer, purchased from AET Corporation of Japan) was used for reference. The method described in JIS C2565 Measuring methods for ferrite cores for microwave device measures each sample to be tested at a frequency of 10GHz. The lower the dielectric constant and the lower the dielectric loss, the better the dielectric properties of the sample to be tested. Differences in Dk values greater than 0.1 represent significant differences between the dielectric constants of different substrates. Under the measurement frequency of 10GHz and the Df value is less than 0.005, the difference of Df value less than 0.0001 means that there is no significant difference in the dielectric loss of the substrate, and the difference of Df value greater than 0.0001 means that there is a significant difference in the dielectric loss of different substrates (There are significant technical difficulties).

[Table 1] Composition of the resin compositions of Examples E1 to E6 (unit: parts by weight)

[Table 2] Composition of the resin compositions of Examples E7 to E13 (unit: parts by weight)

[Table 3] Characteristic test results of the resin compositions of Examples E1 to E6

[Table 4] Characteristic test results of the resin compositions of Examples E7 to E13

[Table 5] Compositions of resin compositions of Comparative Examples C1 to C6 (unit: parts by weight)

[Table 6] Compositions of resin compositions of Comparative Examples C7 to C13 (unit: parts by weight)

[Table 7] Characteristic test results of the resin compositions of Comparative Examples C1 to C6

[Table 8] Characteristic test results of the resin compositions of Comparative Examples C7 to C13

From Tables 1 to 8, the following phenomena can be observed.

First of all, compared with Comparative Example C12 using the vinyl-terminated phosphorus-containing polyphenylene ether resin in Examples E1, E9 to E13 using the phosphorus-containing flame retardant of the present invention in the resin composition, it can be found that Examples E1, E9 to E13 E13 has better prepreg filling, lower dimensional change rate, higher glass transition temperature, better flame retardancy and higher copper foil pull. Compared with Comparative Example C6 using DOPO derivatives, it can be found that C6 has poor flame retardancy. Comparative Example C7 increases the amount of DOPO derivatives used but causes prepreg fillability, alkali resistance, glass transition temperature, and dimensional changes. By comparing Examples E1, E9 to E13 and Comparative Example C7, it can be found that Examples E1, E9 to E13 using the phosphorus-containing flame retardant of the present invention all have better prepreg filling properties, better resistance to Alkaline, higher glass transition temperature, higher copper foil tension, better heat resistance after moisture absorption.

Referring to Examples E1, E9, E10, and E12, compare Example E11 of phosphorus-containing flame retardants synthesized using two phenols, tetraphenolic ethane and diallyl bisphenol A, and three different flame retardants using the present invention. Phosphorus flame retardants (respectively, phosphorus-containing flame retardants synthesized using diallyl bisphenol A, phosphorus-containing flame retardants synthesized using triphenolic ethane, and phosphorus-containing flame retardants synthesized using tetraphenolic ethane, respectively flame retardant) with Example E13, it can be found that Examples E11 and E13 have higher glass transition temperature, lower dielectric constant and lower dielectric loss.

With reference to Example E1, compare Comparative Example C5 in which each reaction component (1,4-p-dichlorobenzyl, diallyl bisphenol A, DOPO-HQ, vinylbenzyl chloride) was added alone, and three groups were used. Parts of the synthesized products of Comparative Examples C1 to C4 and C13, as well as Comparative Example C6 not using the phosphorus-containing flame retardant of the present invention, and Comparative Examples C7 to C12 using other kinds of flame retardants, it can be found that the prepreg of Example E1 is filled with The comprehensive characteristics of adhesiveness, flame retardancy, alkali resistance, glass transition temperature, thermal dimensional stability (that is, the dimensional change rate after heating), heat resistance after moisture absorption, copper foil tension, dielectric constant and dielectric loss are all higher than Excellent, especially unexpected improvement in copper foil tension.

In general, it can be found that the resin composition using the phosphorus-containing flame retardant of the present invention has excellent performance in prepreg fillability, flame retardancy, alkali resistance, glass transition temperature, thermal dimensional stability (ie, dimensional change rate after heating), After moisture absorption, at least one, multiple or all of properties such as heat resistance, copper foil pulling force, dielectric constant and dielectric loss are unexpectedly improved.

The above embodiments are merely auxiliary descriptions in nature, and are not intended to limit the embodiments of the subject matter of the application or the applications or uses of these embodiments. As used herein, the term "exemplary" means "serving as an instance, instance, or illustration." Any illustrative embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

Furthermore, while at least one illustrative or comparative example has been presented in the foregoing embodiments, it should be appreciated that a vast number of variations of the present invention are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, utility, or configuration of the claimed subject matter in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient guide for implementing the described embodiment or embodiments. Furthermore, various changes can be made in the function and arrangement of elements without departing from the scope defined by the claims, which include known equivalents and all foreseeable equivalents at the time of filing this patent application. thing.

Claims (15)

1. A phosphorus-containing compound, represented by the following formula (1):

Wherein, m is an integer from 0 to 50, n is an integer from 2 to 25, and a is an integer from 0 to 23; A and A' each independently represent the group after the dehydrogenation of the hydroxyl group of a dihydric phenol or a polyhydric phenol; B represents the group after dechlorination of the dichloro compound; D represents the group after the dehydrogenation of the hydroxyl group of the dihydric phenol or polyhydric phenol containing DOPO functional group; X independently represents a functional group or hydrogen containing a double bond, and each X is not hydrogen at the same time; Y may be absent, or each independently represents a group represented by the following formula (2), or a hydrogen atom;

Wherein, q is an integer from 0 to 20, and A', B, D, and X are as defined in formula (1). 2. The phosphorus-containing compound according to claim 1, wherein the number-average molecular mass of A and A' is less than or equal to 1200. 3. The phosphorus-containing compound according to claim 1, wherein the A and A' comprise any one of the groups represented by formula (3) to (23) or any combination thereof, wherein p is an integer from 0 to 23:

4. The phosphorus-containing compound of claim 1, wherein the B comprises any one of the groups represented by formula (24), formula (25), and formula (26) or any combination thereof:

5. The phosphorus-containing compound of claim 1, wherein the D comprises any one of the groups represented by formula (27) and formula (28) or any combination thereof: 6. The phosphorus-containing compound of claim 1, wherein the X-containing compounds are each independently any one of the groups represented by formula (29), formula (30), and formula (31): Wherein, R1 to R13 are each independently one or more of a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group; Q is a covalent bond or a functional group having at least one carbon atom. 7. The phosphorus-containing compound according to claim 1, characterized in that it comprises any one of the structural formulas shown in the following formula (32) to (38):

8 . A phosphorus-containing flame retardant, characterized by comprising one or more of the phosphorus-containing compounds according to any one of claims 1 to 7 . 9 . A resin composition comprising the phosphorus-containing flame retardant according to claim 8 and a resin having an unsaturated bond. 10 . 10. The resin composition according to claim 9, wherein the resin having an unsaturated bond comprises divinylbenzene, bisvinylbenzyl ether, 1,2-bis(vinylphenyl)ethane , triallyl isocyanurate, triallyl isocyanurate prepolymer, triallyl cyanurate, triallyl cyanurate prepolymer, 1,2,4 - any of trivinylcyclohexane, vinylbenzylmaleimide, diallylbisphenol A, styrene, acrylate, vinyl polyphenylene ether resin, maleimide resin, and polyolefin species or any combination thereof. 11. The resin composition of claim 9, further comprising epoxy resin, cyanate ester resin, phenol resin, benzoxazine resin, styrene maleic anhydride resin, polyester, amine curing agent, polyamide, polyimide, or any combination thereof. 12. The resin composition according to claim 9, further comprising any one of a flame retardant, an inorganic filler, a hardening accelerator, a solvent, a silane coupling agent, a surfactant, a coloring agent, and a toughening agent species or any combination thereof. 13. The resin composition according to any one of claims 9 to 12, characterized in that it comprises 5 to 40 parts by weight of the phosphorus-containing flame retardant, and 50 parts by weight of the resin having an unsaturated bond parts to 100 parts by weight. 14. An article made of the resin composition according to any one of claims 9 to 12, characterized in that it comprises a prepreg, a resin film, a self-adhesive copper foil, a laminate or a printed circuit board. 15. A method for producing a phosphorus-containing flame retardant, wherein the phosphorus-containing flame retardant comprises one or more of the phosphorus-containing compounds according to any one of claims 1 to 7, the The method includes the following steps: First, the dihydric phenol or polyhydric phenol is reacted with the dichloro compound, and then the metal salt of the dihydric phenol or polyhydric phenol containing DOPO functional group is added for the reaction, and then the vinyl halide is added for the reaction, and the filtration is carried out to obtain the said compound containing Phosphorus flame retardant.

Images